Crystalline zeolite q



United States Patent 2,991,151 CRYSTALLINE ZEOLITE Q Donald W. Breck, Tonawanda, and Nancy A. Acalfa,

Kenmore, 'N.Y., assignorsto Union Carbide Corporation, a corporation of New York No Drawing. Filed Dec. 5, 1957, Ser. No; 700,735

Claims. ((31,2'3-413) This invention relates to a novel composition of matter, and to a process for preparing andutilizingithis novel material. More particularly, thev invention concerned with a novel, synthetic member of the zeolite, family.

The term zeolite, in general, refersto agroup of naturally occurring, hydrated, metal aluminosilicates, many of which are crystalline in structure. The Sy lh ticma- .terial of the invention has a compositionsimil-ar to certain vtetrahedra; The tetrahedra are cross-linkedby the sharing of oxygen atoms, so that theratio ,of-oxygenatoms to the total of the aluminum. and silicon atoms is equal to two, or O/(Al+Si)=2. Thenegative electrovalel ce of tetrahedra containing aluminum isbalanced by the inclusion within the crystal of cations, .e.g., alkal-imetal or alkaline earth metal ions. This balance maybe, expressed by the formula 2Al/ (2Na, 2K, 2Li, Ca,-,Ba,;Sr, etc. -l. Moreover, it has been found that one cation may be, replaced for another by suitable ,exchange v teclmicp es. Consequently, crystalline zeoliteslare often employed, as ion-exchange agents.

It is also known that the crystal structures ofmany zeolites exhibit interstices of moleculardjmensions. ---Ihe interstitial spaces are generally occupied by ,water of, hy-

dration. Under proper conditions, -,viz., after-atleast partial dehydration, these zeolites maybe utilizedas efiicient adsorbents whereby adsorbatemolecules are retained within the interstitial spaces. Accessto these channels is had by way of orifices in the crystal l ttice. These openings limit the. size. and shape; of the molecules that can be adsorbed. A separation of mixtures of. foreign .molecules based upon molecular dimensions, wherein certain molecules are adsorbed by thezeolitewhile others are refused, is therefore possible. It is this characteristic property of many crystalline zeolites. that has led totheir designation as molecular sieves. In addition to molecular size and shape, however, other. factors may also influence the selective adsorptionofgcfi iain foreign molecules by molecular sieves. .Among thesefactors are: the polanizability and polarity oi the adsorbatemql flllcs;

from the naturally occurring materialpn the; basisof their composition, crystal structure, and adsorption properties. A suitable method for distinguishingthesecompounds, for example, is. by their X-ray powder, diflraction patterns. The existence of a number,of zeoliteshail l 2,991,151 Patented July 4, 1961 "ice similarbut distinguishable properties advantageously perthe selectionof a particular member having optimum prope ffie's fora particular use.

The present invention hasas its prime object the pro- ,yisio of a nove syn h cry a in l -te 1the molecular sieve type. Another object is to Q provide f a novel, synthetic, crystalline zeolite haying usefulion- .Xchange and. adsorption properties. A further object is Ito provide a convenient and efiicient process for preparing the novel materialofthe invention.

The composition ofz eolite Qv may stoichiometrically be vexpressedin terms of mole ratios of oxides. Thus, a 'ge n eral formula for zeolite Q may be represented as fol- 0.95 :i:0.05M 0.AlflOzZZ-ZiO-05SlO2ZZH3O 'fi wherein M designates at least one exchangeable cation,

las'jhereinbelow defined, n;repr esents the valence of 20 ;Minor variations in the mole ratios of these oxides, within the rangesindicated by the above formula, do not Mfptmd fx may be any value from 0 to about S.

significantly change the crystal structure or physical properties of the zeolite. Likewise, the value of x is not n'ecessarily an invariantfor all samples of zeolite Q; This isftrue because various exchangeable cations are of'difjferent size, and as no appreciable modification of the crystal lattice dimensions of the zeolite is effected "by the exchange of these particular cations, more or less interstitial space should be available for the accommodation of water molecules. The value of x therefore "depends upon the identity of the exchangeablecation, and also uponthe degree of dehydration of the zeolite.

"The exchangeable cations contemplated by the present invention include monoand divalent metal ions, particularly thoseofgroups I and ll of the periodic table, as set forth in Websters New Collegiate Dictionary, 1956 edition, page 626, such as barium, calcium, lithium, mag- 'nesium,,potassium, sodium, strontium, zinc ions etc., and

jthejlilcejandother cations, for example, hydrogen and ions, which, with zeolite Q, behave like' -the metal ions mentioned aboveinthat theymay be replaced for other exchangeable cations without causing a substan- 1; tiallalteration'of the basic crystal structure of the zeolite. 45

,thatmay bepresent in zeolite Q, itis preferred to syngthesizethe potassium formof the zeolite, i.e., theform 'in which potassium ions are included as the exchangeable cation. The reactants accordingly, employed are readily available and generally water soluble. jions in the potassium form of, zeolite Q may their con veniently be replaced by other exchangeable cationsj as ,willbe shown below, thereby yielding isomorphicforms ofthe zeolite.

form of zeolite Q is prepared by suitably heating'an aqueous potassium aluminosilicate mixturewhose'com- Although there are a number of exchangeable cations The potassium f In an embodiment of the present invention, the potasposition, expressed in terms of mole ratios'of oxides, falls uwherebythet desired prodnct is crystallized out.

; In making the potassium form of zeolite Q, representa- -;--tiye reactants are silica gel, silicic acid, or potassiunr sili- ,gate asa source of silica. Alumina may be obtained from activated alumina, alpha alumina, gamma alumina, alumina trihydrate, aluminum hydroxide, or potassium alurninate. Potassium hydroxide may supply the potassium ions, and, in addition, assist in controlling the pH of the reactant mixture. Preferably, the reactants are water soluble. A solution of the reactants, in proper proportions, is placed in a container, made, for example, of metal or glass. The container should be closed to prevent loss of water. A convenient and preferred procedure for preparing the reactant mixture is to make an aqueous solution containing the potassium aluminate and hydroxide, and add this, with agitation, to an aqueous solution of potassium silicate. The resultant mixture is then stirred to insure homogeneity.

For best results, the crystallization procedure is carried out at a temperature of approximately 50 C. The potassium form of zeolite Q may, however, be satisfactorily prepared at temperatures of from about 25 C. to about 50 C., the pressure being atmospheric, or at least that corresponding to the vapor pressure of water in equilibrium with the mixture of reactants at the higher temperature. Any suitable heating apparatus, e.g., an oven, sand bath, oil bath, or jacketed autoclave, may be used. Heating is continued until the desired crystalline zeolite product is formed. The zeolite crystals are then filtered ofi and washed to separate them from the reactant mother liquor. The zeolite crystals should be washed, preferably with distilled Water, until the effiuent wash water, in equilibrium with the product, has a pH of between about 9 and 12. As the zeolite crystals are washed, the exchangeable cation of the zeolite may be partially removed, and is believed to be replaced by hydrogen cations. If the washing is discontinued when the pH of the effluent wash water is about 10, the K O/A-l O molar ratio of the crystalline product will be between about 0.9 and 1.0. Excessive washing will result in a somewhat lower value for this ratio, while insufficient washing may leave slight excesses of potassium associated with the product. Thereafter, the zeolite crystals may be dried, conveniently in a vented oven. The product is thereby obtained having a composition, expressed in terms of mole ratios of oxides, corresponding to the formula:

0.95i0.051201A1203 I I xH O wherein x may be any value from to about 5.

Typical of the manner in which the potassium form of zeolite Q may be prepared is the following example. A solution of potassium aluminate was prepared by initially mixing 32.2 grams of potassium hydroxide, 3 grams of aluminum hydroxide containing 0.0492 mole of A1 0 and 42.6 ml. of water, and heating the mixture until the reactants dissolved. The solution was then cooled to room temperature, and added to 23.7 grams of a potassium silicate solution containing 7.8 percent of K 0 and 19.3 percent of SiO by weight. The resulting mixture was stirred until homogeneous. Crystallization of the desired zeolite product was carried out by heating the reactant mixture in a sealed glass jar at a temperature of 50 C. for approximately 162 hours. The crystalline product which formed had thereupon settled to the-bottom of the jar, and the reactant mother liquid was clear. The crystalline product was then filtered, washed with water until the efiiuent wash water had a pH of about 10.5 to 11.0, and dried. Analysis of the product showed it to be a zeolite having a composition, expressed in terms of mole ratios of oxides, corresponding to the formula:

0.99K O A1 0 2. 17Si0 5H O The replacement of the exchangeable cation present in zeolite Q at least in part by othercations may be accomplished by conventional ion-exchange techniques. A preferred, continuous method is to pack zeolite into a series of vertical columns with suitable supports at the bottom; successively pass through the beds, at room temperature,

a water solution of a soluble salt of the cation to be introduced into the zeolite; and change the flow from the first bed to the second as the zeolite in the first bed becomes ion-exchanged to the extent desired. To obtain hydrogen exchange, for example, a dilute water solution of an acid such as hydrochloric acid is effective as the exchanging solution. For sodium exchange, a water solution of sodium chloride or dilute sodium hydroxide is suitable. Other convenient reagents are: for potassium exchange, a water solution of potassium chloride or dilute potassium hydroxide; for lithium, barium, calcium, magnesium, strontium, zinc, ammonium exchange, and the like, water solutions of the chlorides, sulfates, or nitrates of these cations. While it is more convenient to use water soluble compounds of the exchangeable cations, other solutions containing the desired cations may also be employed. Moreover, particularly good results may be obtained by the utilization of an exchanging solution having a pH of between about 5 and 12.

In a typical exchange, 7.5 grams of the potassium form of zeolite Q, obtained as heretofore described, were admixed with an aqueous solution containing 5.85 grams of sodium chloride in ml. of water. The mixture was stirred for about one-half hour, and allowed to stand overnight. Upon standing, the Zeolite crystals were filtered, and the exchange process repeated as described above. The zeolite crystals were then refiltered, washed with distilled water, and dried. Analysis of the product indicated that approximately 65 percent of the potassium ions had been replaced by sodium ions. In other exchanges, conducted in a similar manner, 7.5 grams of the potassium form of zeolite Q were treated with the following solutions: (a) 6.4 grams of lithium sulfate monohydrate in 100 ml. of water, resulting in the exchange of approximately 58 percent ofthe potassium ions in the zeolite by lithium ions; (b) 5.55 grams of calcium chloride in 100 ml. of water, resulting in the exchange of approximately 81 percent of the potassium ions in the zeolite by calcium ions; (0) 10.15 grams of magnesium chloride hexahydrate in 100 ml. of water, resulting in the exchange of aproximately 45 percent of the potassium ions in the zeolite by magnesium ions; (d) 14.85 grams of zinc nitrate hexahydrate in 100 ml. of water, resulting in the exchange of approximately 64 percent of the potassium ions in the zeolite by zinc ions; (e) 13.35 grams of strontium chloride hexahydrate in 100 ml. of water, resulting in the exchange of approximately 64 percent of the potassium ions in the zeolite by strontium ions; and (f) 12.2 grams of barium chloride dihydrate in 100 ml. of water, resulting in the exchange of approximately 66 percent of the potassium ions in the zeolite by barium ions. I

In addition to composition, zeolite Q may be identified and distinguished from other zeolites, and other crystalline substances, by its X-ray powder diffraction pattern, the

data for whichare set forth below in Tables A and B.

In obtaining the X-ray powder diffraction patterns, standard techniques were employed. The radiation was the K- alpha doublet of copper, and a Geiger counter spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of 20, where 0 is the Bragg angle, were read from the spectrometer chart. From these, the relative intensities, 1001/ I where I is the intensity of the strongest line or peak, and d (A.) observed, the interplanar spacing in Angstrom units, corresponding to the recorded lines were determined.

X-ray powder diffraction data for a sample of the potassium form of zeolite Q (K Q) and for isomorphic forms of the ezolite in which varying amounts of the potassium ions have been replaced by other exchangeable cations, as heretofore described, viz. a 65 percent sodium exchanged zeolite Q (Na Q), a 58 percent lithium exchanged zeolite Q (Li Q), an 81 percent calcium exchanged zeolite Q (CaQ), a. 45 percent magnesium exchanged zeolite Q (MgQ), a 64 percent zinc exchanged zeolite Q (ZnQ), a 64 percent strontium exchanged zeo- Thus, zeolite Q may be defined as a synthetic, crystalline aluminosilicate having .an X-ray powder diffraction pattern characterized by at least those interplanar spacing values as set forth in Table B.

Occasionally, additional lines not belonging to the pattern for zeolite Q appearrin a pattern along with the X- ray lines characteristic ofizeolite Q. This is an indication that one or more additional crystalline materials are mixed with zeolite Q in the sample being tested. The particular X-ray technique and/or apparatus employed, the humidity, the temperature, the orientation of the powder crystals, and other variables, all of which are well known and understood to those skilled in the art of X- ray crystallography or diffraction, may also cause some variations in the intensities and positions of the X-ray lines. Thus, the X-ray data given herein to identify zeolite Q are not to exclude those materials which, due to some variable mentioned above or otherwise known to those skilled in the art, fail to show all of the tabulated X-ray lines, or show a few extra ones that are permissible to the crystal system of the zeolite, or show a slight change in intensity or shift in position of some of the X-ray lines.

For satisfactory use as an adsorbent, zeolite Q should be activated by at least partial dehydration. Such activa: tion may be performed, for example, by heating the zeolite to temperatures of approximately 130 C. under atmospheric or reduced pressure, or by maintaining the zeolite at room temperature under vacuum. Unlike common adsorbents, such as charcoal and silica gel, which show adsorption selectivties based primarily on the boiling point or critical temperature of the adsorbate, ac tivated zeolite Q exhibits a selectivity based on the size, polarity, degree of unsaturation, and shape of the adsorbate molecule. Adsorption by zeolite Q is generally limited to small, polar molecules.

Another property of zeolite Q which contributes to its usefulness is that of adsorbing relatively large quantities of adsorbate at either very low pressures or concentrations. The novel material of this invention may therefore be utilized as a selective adsorbent in numerous gas or liquid separation processes, whereby small, polar molecules, particularly water, are separated from mixtures with other materials. The zeolite may also find use in cyclic adsorption-desorption processes for water, and possibly other adsorbates.

Samples of the potassium form of zeolite Q which had been activated by dehydration at a temperature of approximately 130 C., under vacuum, were tested. to determine their adsorption properties. The results obtained are set forth below in Table C. The adsorption properties were measured in a McBain adsorptive system. The zeolite samples were placed in light aluminum buckets suspended from quartz springs. They were activated in situ, and the gas or vapor under test was then admitted to the system. The gain in weight of the adsorbent was Table C Tempera- Pressure Weight Adsorbate ture 0.) (mm. Hg) Percent 5 Adsorbed -3 2: H1O 25 4. 5 11. s 25 18.3 0. 01:5;

' e e 12 5. 8 CO1 25 97 6 385 8. 5 720 9. 7 0.15 1.3 a a 16 25 142 5.3 338 6. 2 694 6. 9 0.09 2.2 4 2.9 12 3.9 801 25 314 5. 5 721 6.3 24 0.6 196 400 1.4 710 2. 5 85 1. 6 l 120 1. 4 196 93 l. 6 25 700 0 25 700 O 25 700 0 From Table C, it may be seen, for example, that the activated potassium form of zeolite Q, acting as a molecular sieve, may permit the separation of small, polar molecules such as those of water, carbon dioxide, ammonia, or sulfur dioxide from a mixture with other molecules, such as those of nitrogen, oxygen, argon, ethane, ethylene or propylene.

Other isomorphic forms of zeolite Q may also be employed as efficient adsorbents for small, polar molecules as illustrated by the adsorption data outlined in Table D, below. The data were obtained in tests utilizing samples of zeolite Q in which varying amounts of the potassium ions had been replaced by other exchangeable cations, as heretofore described, viz. a 65 percent sodium exchanged zeolite Q (Na Q), a 58 percent lithium exchanged zeolite Q (Li Q), and 81 percent calcium exchanged zeolite Q (CaQ), a 45 percent magnesium exchanged zeolite Q (MgQ), a 64 percent zinc exchanged zeolite Q (ZnQ), a 64 percent strontium exchanged zeolite Q (SrQ), and a 66 percent barium exchanged zeolite Q (BaQ). The samples were activated prior to adsorption by dehydration at a temperature of approximately 130 C., under vacuum, and the adsorption properties measured in a manner similar to that described above for the potassium form of zeolite Q. In Table D, the pressure given for each adsorption is the pressure of the adsorbate. The term weight percent adsorbed refers to the percentage increase in the weight of the adsorbent.

Table D Weight Percent Adsorbed Adsorbate Temp. Pressure 0.) (mm. Hg)

NazQ, LnQ CaQ MgQ ZnQ SrQ BaQ 25 25 22. 3 27. 0 20. 7 21. 9 25. 4 10. 8 17. 0 25 700 4. 7 12.1 11.8 0. 8 12.5 11.3 7. 9 25 700 5. 8 9.1 12.2 11.3 15. 8 25 700 0 0 5. 1 2. 3 5. 8 4. t) O. 4 -196 1.1 3.0 6. 9 2. 8 6.0 4.1 1. 4 25 700 0 0 7. 8 1. l 7. 0 25 700 0 4. 5 26. 5 20. 8 22. 3 22. 2 5. 4 l96 700 0 2.3 3. 2 2.6 4. 8

measured by the spring extensions as read by a cathetometer. In Table C, the pressure given for each adsorption is the pressure of the adsorbate. The term weight percent adsorbed refers to the percentage increase in the weight of the adsorbent.

The results illustrated above in Table D indicate that, as in the case of the potassium form of zeolite Q, isomorphic, ion-exchanged forms of the zeolite generally permit the adsorption of only small, polar molecules.

5 However, the maximum size for adsorbate molecules,

i9 may, in'rthe -latter. instances,: "bev less..narrow1 y.-limited, .as compared to those adsorbed by the potassiurmformmfizeolite Q.

Zeolite Q may be used as an adsorbent for the purposes indicated above in any suitable form. For example, a

column of powderedcrystalline material may give excellent results as may'afp'elletedform obtained by pressing into pellets a mixture of zeolite Q and a suitable bonding agent such as clay.

What is claimed is:

l. A synthetic; crystalline zeolite having a composition, expressed in terms 0f-::m01e ratios of oxides, as follows:

fin

whereinM represents at least'one zexchangeable cation selected from the group consisting of .metal ions of groups I and II of the periodic table, 'hydro gen ions, and ammonium ions, and x is any' va'lueifrom 0 to about 5,

said synthetic, crystalline zeolite'having an X-ray powder diffraction pattern essentially as'shown in Table B.

Table'tB 1 60010.06 4.7s10.0s 4.441005 4.18i0.05- 3.721002 13.681001 3.351004 3.271002 3.131002 30010.03 2.921003 2. A synthetic, crystalline zeolite according to claim 1, wherein at least .a substantial portion of the exchangeable cations are potassium ions, said crystalline zeolite having an X-ray powder diifraction pa'tternaasentially as shown in Table A:

ThbleJA d(A.) SITIIOOI/Ig .413. .347 "11. 1 *100 ..6. 1 3 6. 7 .n. .11 6 4 4 l I: 8

i1 0 .-A. synthetic. crystallinezeoliteaaccordingato claimlr1, wherein at least a substantial portion of the exchangeable cations are sodium ions,r saicl .crystalline zeolite having an X-ray powder diffraction pattern essentially as shown in Table A:

"4. A synthetic, crystalline zeolite ac'cording-to claim 1, wherein 'at' leasba substantial portion-of the=exehangeable cations are lithium ions, said crystalline zeolite havingan X-ray powder difiraction pattern essentially as shown in Table A:

Table A LlsQ A pisA synthetic cr-ystalline zeolite according tolclaim l,

hereinatrleast a substantial portionv of'the exchangeable cations-are. barium ions, said crystalline zeolite; havipgan 1 1- i 12 X-ray powderdiflraction pattern essentially asshown in having" an X-ray powder difiraction pattern essentially as Table A: r shown in Table A: 7 TableA I V h f; V TableA 6 Eat; 7

13.4 45 11.3 100 13.8 41 9.30 3 11.9 100 s. 93 10 1.13 3 3.15 13 3. 93 20 3.02 19 6.80 53 5.19 10 0.03 30 5.31 3 5.90 20 4.11 10 5.31 21 1 4.44 13 4.11 r 13 4.21 29 4.43 3.12 29 4.23 21 3.39 23 3.14 33 3.31 24 3.31 13 3.29 13 3.39 '40 3.25 16 3.25 13 3.15 32 20 3.01 52 3.15 13 2. 92 29 3.02 53 2.31 23 2.94 21 2.33 10 2.39 20 2.55 13 2.33 13 2. 49 13 2.55 20 2. 1g :31: 2:21 10 2.14 10 2.22 13 2.10 10 2.14 '1 2.10 13 v r 8. A synthetic, crystalline zeolite according to claim 1, wherein at least a substantial 'portion of the exchangeable cations are strontium'ions, said crystalline zeolite having an X-ray powder diffraction pattern essentially as shown in Table A: 6. A synthetic, crystalline zeolite according to claim 1, 5 7 Table A wherein at least a substantial portion of the exchangeable Q cations are calcium ions, said crystalline zeolite having 7 an X-ray powder diffraction pattern essentially as shown 0 5 in Table A: 5

"3'93" "'it'f" 3.10 32 Table A 3i 5.34 14 9 ill 33 *3 3 1001/10 31 31 i4 22 3 42 3125 24 11.6 100 3 4 29 9 3.00 100 35 2.92 33 5. 94 15 2 7 33 12 2.32 19 6 2. 54 33 iii i3 '55 24 g3 g3 -f'fiif--. g g; 13 iii l 3125 10 209 3 3 3 3 65 24 9. A synthetic, crystalline zeolite having a composition, g-gg expressed in terms of mole ratios of oxides, as follows: 33% g 0.95 i0.05K O:A1 O :2.2 :0.05SiO,:xH O 3; 3 65 wherein x is any value from 0 to about 5, said synthetic, 3. g crystalhne zeolite having an X-ray powder diffraction pattern essentially as shown in Table B:

" Table B 11.75:0.15 -7 Aisynthetic;crystalline zeolite according to claim 1, 7.00:0.15 wherein atleast apsubstantial portion of the exchange- 'able cations are magnesium ions, said crystalline zeolite 75 6.00:0.06

follows:

mear; 1:5 1

' l 3.72% 0.02 3*:68i0-01 1 3:35 $0.04 1 33110.02 1 3:1"3 $0.02 l 3.00$0.03 2.92% 0.03 $6720.02 aszaaoz I 2.54-'l*:0.02

10. A synthetic, crystalline zeolite having a composition, expressed in terms ofttnole ratios of oxides, as

dissessomea150,.rzronssio sngo wherein x" is any valuefi'om"0 tdabout 5, said synthetic, crystalline zeolite liaviiig an X-rayp'owder diffraction pattern essentially as sliownin Table A:

Table A 11. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

wherein x is any value from 0 to about 5, said crystalline zeolite having an X-ray powder diffraction pattern essentially as shown in Table B Table B which process comprises preparing an aqueous potassium ?10 aluminosilicate mixture whose-"composition, expressed in terms of'mole ratios of oxides; falls within the following ranges:

KQO/SiO, of about 4 ofabout 4 Hie/K20 of abOllt 12 and maintaining such mixture at a temperature of between about 25 Ci and about 50 C. until the desired crystalline zeolite product is formed.

12. A process for preparing a'orystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

wherein X -:is' -any value x from 0 to: about 5,=. -said-crystalline zeolite having an X-ray powder difiractiommattern essentially as showninTable-I'B Table *8 13510.2 umsija s mos-30.15 6.72:0.08 szoogaos rns- 0.05

3.72:0.02 33.68-20.01 31ss=oao4 34130.02 321320.02 :zaooiaos .zsziozos 2.67:0.02 2.62:0.02 2.54:0.02 2.10:0.01

which process comprises preparing an aqueous potassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides, falls within the following ranges:

K O/SiO of about 4 SiO /AI O of about 4 H O/K O of about 12 maintaining such mixture at a temperature of about 50 C. until the desired crystalline zeolite product is formed, and separating the resulting crystals from the reactant mother liquor.

13. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

0.95$0.05K O:Al O :2.2$0.05Si0,:xH,0

wherein x is any value from 0 to about 5, said crystalline zeolite having an X-ray powder difiraction pattern essentially as shown in Table A Table lODI/Io which process comprises preparingan' aqueous potassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides falls within the following ranges:

x o/sio'gai'about t A13Q3 Of about 4 H p/K50 of about 12 maintaining such mixture at atemiperature of about 50 C. until the desired crystalline zeolite product is formed, and separating the resulting crystals from the reactant mother liquor. I

14. A process for preparing a crystalline zeolite having a composition expressed in terms of mole ratios of oxides, as follows: A

09914 01141565 z nsio sn o said crystalline zeolite having X-ray powder diflraction pattern essentially as show n i n Tab1e B:

. T abl eT B 7 16 '-7.00:0.15 6.722008 6.00:0.06 4.75i0.05 4.44:0.05 4.18i0.05 3.721%].02 3.68:0.01 3.35:0.04 3.27:0.02 11310.02 3.00:0.03 2.92:0.03 2.67:0.02 2.62i0.02 2.54:0.02 2.10:0.01

which process comprises preparing an aqueous potassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides is maintaining such mixture at a temperature of about 50 C. until crystals are formed having the desired composition, and separating the crystals from the reactant mother liquor.

15. A process according to claim 11 which includes activating said crystalline zeolite product by heating such product to a temperature of about 130 C. under dehydrating conditions whereby the evolved water of hydration is carried away.

References Cited in the file of this patent UNITED STATES PATENTS 2,283,172 Bates May 19, 1942 2,882,244 Milton Apr. 14, 1959 FOREIGN PATENTS 777,233 Great Britain June 19, 1957 OTHER REFERENCES Kumins et al.: Ind. and Eng.'Chem. 45, pages 57-72 Mellor: Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 6, part 2, page 568, first para. 

0.95$0.05M O:AL2O3:2:2$0.05SIO2:XH2O 2/N
 1. A SYNTHETIC, CRYSTALLINE ZEOLITE HAVING A COMPOSITION, EXPRESSED IN TERMS OF MOLE RATIOS OF OXIDES, AS FOLLOWS: 13.6$0.2 111.75$0.15 7.00$0.15 6.72$0.08 6.00$0.06 4.75$0.05 4.44$0.05 4.18$0.05 3.72$0.02 3.68$0.01 3.35$0.04 3.27$0.02 3.13$0.02 3.00$0.03 2.92$0.03 2.67$0.02 2.62$0.02 2.54$0.02 2.10$0.01 